Noncovalent aromatic molecules

It often becomes necessary to prepare dispersions of graphene in organic or aqueous media [73-74]. For this purpose, different approaches have been successfully employed for few-layer graphene. The two main approaches for obtaining this type of graphene are covalent functionalization or by means of noncovalent interactions. There has been some recent effort to carry out covalent and noncovalent functionalization of graphene with aromatic molecules, which help to exfoliate and stabilize the individual graphene sheets and to modify their electronic properties [75 84]. 

Noncovalent interactions in metal complexes of biomolecules may play an important role in the creation of supramolecular structures around the metal center. For instance, extensive three-dimensional hydrogen-bonded stmcmres grow around metal complexes of barbiturates, recognized as the most widely used drugs for the treatment of epilepsy.Electrostatic interactions between a cation and the Trring of an aromatic molecule (cation-tt interactions) are common motifs in protein structures. Little is known about alkali and alkali-earth cation-tt inter-... 

In ESI-MS, a wealth of noncovalent ion/molecule adduct ions can be also generated. For instance, the formation of ion/solvent (So) adducts, [M + So]+, were observed during ESI-MS of 3-hydroxyaniline as well as other aromatic molecules. The relative abundances of ions [M + H]+, [M + So + H]+ and [M + 2 So + H]+ were studied as a function of the temperature and pH, with the solvents being mixtures of methanol/water and acetonitrile/water sometimes containing ammonium acetate as additive118. 

Some aromatic molecules, such as pyrene, porphyrin, and their derivatives, have strong affinity with the basal plan of graphene sheets via n-n interactions. Noncovalent functionalization has been used in the functionalization of CNTs, and as the rise of graphene, it has been used for functionalization of graphene. 

A simple binding between small molecules and DNA occurs by the process of intercalation. Intercalative binding involves a noncovalent interaction that results from the insertion of the small molecules between the base pairs of the DNA helix. Intercalation commonly occurs with flat aromatic molecules that are held perpendicular to the axis of the DNA helix. Metal complexes with aromatic ligands can intercalate into DNA. ... 

As a final example we consider noncovalent molecular complex formation with the macrocyclic ligand a-cyclodextrin, a natural product consisting of six a-D-glucose units linked 1-4 to form a torus whose cavity is capable of including molecules the size of an aromatic ring. Table 4-3 gives some rate constants for this reaction, where L represents the cyclodextrin and S is the substrate ... 

The alternative noncovalent functionalization does not rely on chemical bonds but on weaker Coulomb, van der Waals or n-n interactions to connect CNTs to surface-active molecules such as surfactants, aromatics, biomolecules (e.g. DNA), polyelectrolytes and polymers. In most cases, this approach is used to improve the dispersion properties of CNTs [116], for example via charge repulsion between micelles of sodium dodecylsulfate [65] adsorbed on the CNT surface or a large solvation shell formed by neutral molecule (e.g. polyvinylpyrrolidone) [117] around the CNTs. 

Encapsulation of different entities inside the CNT channel stands alone as an alternative noncovalent functionalization approach. Many studies on the filling of carbon nanotubes with ions or molecules focus on how the presence of these fillers affects the physical properties of the tubes. From a different point of view, confinement of materials inside the cylindrical structure could be regarded as a way to protect such materials from the external environment, with the tubes acting as a nanoreactor or a nanotransporter. It is fascinating to envision specific reactions between molecules occurring inside the aromatic cylindrical framework, tailored by CNT characteristic parameters such as diameter, affinity towards specific molecules, etc. 

The large aromatic and hydrophobic character of CNTs make them ideal surfaces for noncovalent interaction vfith molecules via Van der Waals, 7t-stacking or hydro-phobic forces [39, 44]. 

S. K. Burley and G. A. Petsko cover the field of noncovalent interactions of proteins, with particular emphasis on weakly polar interactions. Their presentation of the whole field of electrostatic interactions should be of value to many workers in protein chemistry, but their special concern is with the weaker, but very important, interactions involving aromatic side chains, their orientation relative to one another, to oxygen and sulfur atoms, to amino groups, and to aromatic ligands that may bind to the protein. These interactions, only recently recognized for their influence on protein structure, play an important part in the formation of aromatic clusters in the interior of globular proteins and in other features of structure. The authors provide numerous illustrations of the principles involved, from recently determined structures, of both small molecules and proteins. 

Noncovalent interactions with belt- or tube-like host molecules might also be suitable to a separation of carbon nanotubes by diameter. Cyclodextrines or beltshaped aromatic compounds could be named as examples here. They may not have proven their applicability as selective complexing agent yet, but considering their geometry reveals favorable dispositions for a discriminative interaction with certain nanotubes. Supramolecular arrangements with carbon nanotubes are also discussed in Section 3.5.7. 

Many recents studies have focused on applications of metallointerca-lation, which is also an important noncovalent interaction of metal complexes with nucleic acids. Intercalation is a common mode of association of small molecules with DNA, where a flat aromatic heterocyclic moiety inserts and stacks in between the DNA base pairs (13). Lippard and coworkers (14) determined in 1974 that platinum(II) complexes containing an aromatic heterocyclic ligand such as terpyridine could intercalate in DNA. Figure 2c shows such a stacking interaction of such a complex in a dinucleotide (15). Recently, we have found that intercalation is not restricted to completely flat, square planar complexes, but partial intercalation of ligands coordinated to octahedral metal centers is feasible as well... 

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